Dyestuffs of the triphenylmethane series and process of making same.



.UNTED s rn rus PnaEN'r OFFICE.

AUGUST STOCK AND FRIEDRICH HEIM, or nocns'r-on'rrtnagnm, GERMANY. AS- srenons TO FARBWEBKE VORM. MEISTER LUCIUS & BBijNING, or nocns'r-ou- THE-MAIN, GERMANY, A. QQRPQB'ATION 0F. GEBMAW- DYESTUFFS OF .THE TRIPHENYLMETHANE SERIES PBQGESS 9F MAKING SAME.

No Drawing.

To all whom it may concern.

'Be it lmown that We, AUGUST S'rooK, Ph. D., chemist, and FRIEDRIC HEIM, Ph. D., chemist, citizen ot the Empire of. Germany, residing at Hochst-on-the-Main, Germany, have invented certain new and useful Im-- prove'ments in Dyestufi's of the Triphenylmethane Series and Processes of Making Same, of which the following'is a specification. 9

As described in our U. S. Patent No. 995% and in our U. S. patent application Ser. filo. 578649 filed Qetth August 1910, there are obtained dyestutls of the triphenylmeth-' ane series capable of being subsequently chromed, by heating with an aromatic base the dyestufi's produced by condensing a p -halcgenbenzaldehyde, or a substitution, product, thereof with an ortho-oxyarylcarboxylic acid, and subsequently oxidizing the '7 condensation product. For the preparation of these condensation-products, there were hitherto used only 0 oxycarboxylic acids having the para-position free, so that the condensation with the aldehyde occurred in para-position to the hydroxyl group. Now according to our present invention one molecule of the said o-oxycarboxylic acid may be replaced by such a molecule wherein the para position is occupied, so that there may be used as parent material asymmetrical condensation-products in which the reaction. of the aldehyde with the oxycarboxylic acid has occurred on the one hand in para-positicn, and on the other hand ortho-position, to the hydroxyl group of the oxyarylcarboxylic acid. The said parent material has the following general formula H o l I ocos Ll? mg \H \1!i H HO-I 1 GOOH wherein Hlg stands for a halogen atom, and wherein the hydrogen-atoms of the nuclei may be substituted: acids-which are substituted in para-position are, for in- Specification of Letters Patent.

Pat nted June 24, 1913.

' Application filed July 3 1912- mm 711401 stance, p cresotinic acid, p chlorsalicylic acid, p-chlor-m-cresotinic acid, 2.3-oxynaphthoic acid.

The new. dyestuffs ,have the general formula:

When dry, they form dark powders soluble in caustic alkalis to red' to violet-red solutions; on adding acetic acid they are precipitated. from these solutions in violet to blue fl akes. 'lheir solution in concentrated sulfuric acid is yellowish-red and yields, on.

adding water, violet to blue flakes The dyeings on wool in an acid bath are of a dull grayish-violet tint and when subsequently chromed they turn pure violet to blue; these dyeings are of excellent fastness to washing and milling.

Example: One part of he. product, obtained in the usual manner by condensing equal molecular'proportions of p-chlorbenzaldehyde, m-cresotinic acid, and p-cresotinic acid and subsequently oxidizing, is

heated to 120 C. for f1 hour with 5 parts of anilin and one part of anilin hydrochlorid. The m'assis then poured into an excess of diluted hydrochloric acid for pre cipitating the 'dyestufi" which is then filtered, washed and dried, The dyestufi has the formula:

coon y H H k; l n 1 CsH5-N I n HH O.H

cn coon I It gives dyeings which, after being chromed,

tint than those pro- 8. Patent No. 995,494 p-chlorbenzaldehyde are of a much .greener duced accord ng to U. by the combination of with 2 molecular proportions of m-cresotinic i acid.

Having now described our invention, what, we claim is:

1. T he process of manufacturing dyestuffs of the triphenyluiethane series, capable of being subsequently chromed, which consists in heating with an aromatic base a dyestuff of the general formula:

29 wherein Hie stands for a halogen atom. 2. As new products, the dyestuffs of the riwltw u liorinula wherein R stands for an aryl residue being, when dr dark powders soluble in caustic alkalis to red to violetred solutions from which on the addition of acetic acid they are precipitated in violet to blue flakes, their solution in concentrated sulfuric acid being i yellowish-red yielding violet to blue flakes on addition of water, dyeing wool dull violet to blue tints and, on being subsequently chromed, pure violet to blue tints of great fastness.

3. As a new product, the dyestuil' of the formula:

fiopies of this patent may be obtained for five cents each, by'addressing' the Commissioner of Patents,

' Washington, D. G. 

